CN102883791A - Methods for removing contaminants from natural gas - Google Patents
Methods for removing contaminants from natural gas Download PDFInfo
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- CN102883791A CN102883791A CN2011800225156A CN201180022515A CN102883791A CN 102883791 A CN102883791 A CN 102883791A CN 2011800225156 A CN2011800225156 A CN 2011800225156A CN 201180022515 A CN201180022515 A CN 201180022515A CN 102883791 A CN102883791 A CN 102883791A
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
- B01D53/0476—Vacuum pressure swing adsorption
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- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Abstract
A method for removing contaminants from natural gas streams. The natural gas stream is fed to a dryer, then a membrane module and a multibed, multilayer vacuum swing adsorption process for removal of oxygen, nitrogen and carbon dioxide from the natural gas stream. Alternatively when carbon dioxide is in relatively low concentration in the natural gas stream, the membrane module step is not employed.
Description
The cross reference of related application
The application requires the priority of the U.S. Provisional Patent Application sequence number 61/331,970 of submission on May 6th, 2010.
Background technology
The present invention relates to a kind of method of removing dusty gas such as oxygen and nitrogen from natural gas.More specifically, the invention provides a kind of from natural gas multistage removing dusty gas, such as the method for carbon dioxide, oxygen and nitrogen.
Known to underground reservoir extraction natural gas.Natural gas will comprise the gas that nitrogen and oxygen and other are considered as impurity usually.These pernicious gases can be natural product or the results of such technique, as nitrogen being injected reservoir technique as what improve an oil recovery part.
Early stage technique has attempted removing these dusty gas from natural gas.For example, pressure-variable adsorption (PSA) technique is by two independent PSA stage separating hydrogen gas from natural gas, and the phase I is used for nitrogen, and second stage is used for hydrogen.Mode is used such PSA technique as an alternative, and it utilizes two independent PSA stages.Phase I is removed hydrocarbon from natural gas, and second stage is removed nitrogen.In diverse ways, by the methane of from raw natural gas and solid waste rubbish waste gas, gathering of working continuously of PSA step, to remove VOC.This air-flow is fed to the film system, removes carbon dioxide from natural gas flow thus.
Yet these techniques can't sweep off oxygen and nitrogen from natural gas flow, and they do not remove great amount of carbon dioxide yet, are so that natural gas is essential as fuels sources and remove this tittle.
Summary of the invention
The invention provides a kind of method from natural gas flow removing dusty gas, it comprises that the natural gas flow that will comprise pollutant is fed to drier, membrane module and Vacuum Pressure Swing Adsorption (VSA) system.
More specifically, the invention provides from natural gas flow and clear the pollution off, it may further comprise the steps:
The natural gas flow that a) will comprise pollutant is fed to drier, and this can be pressure-variable adsorption (PSA) or Temp .-changing adsorption (TSA) technique;
B) dry natural gas is flow to be given to membrane module, remove carbon dioxide and oxygen at this from this natural gas flow; And
C) natural gas flow is fed to many beds, multi-layer vacuum pressure swing adsorption system, wherein removes carbon dioxide, nitrogen and oxygen from this natural gas flow.
The pollutant that is present in the natural gas is oxygen, nitrogen and carbon dioxide.The amount of these gases in natural gas is mainly the oxygen of 0-5 molar percentage; The carbon dioxide of the nitrogen of 5-15 molar percentage and 30-45 molar percentage.
Step PSA or TSA technique a) will be removed water from natural gas flow.Usually, in the adsorption bed of PSA or TSA system, can there be sorbing material, such as activated alumina.
Step b) membrane module will sweep off carbon dioxide.In one embodiment, use single group film, and in different embodiment, after first group, add second group of film.This second group of film will further be removed the amount of carbon dioxide that exists in natural gas flow.Also can use specific film, such as modification doughnut polyamide nitrogen film, be present in the oxygen up to half in the natural gas with removing.This will be reduced in needs the amount of oxygen removed in the subsequent step.
At step c), many beds, multilayer VSA system will comprise four adsorption bed usually.Yet, depend on that amount of pollutant and the power cost in the natural gas flow considered, can utilize more or less adsorption bed.Each adsorption bed is carried out stacked to be used for removing carbon dioxide, nitrogen or oxygen.In order to remove carbon dioxide, use the 13X molecular screen material.In order to remove nitrogen, use the titan silicate molecular screen material.Use has high carbon molecular sieve to oxygen affinity or other materials as the 3rd layer, and can be by by step b) membrane module remove how much oxygen and determine this material.
In further embodiment of the present invention, when when carbon dioxide in natural concentration is low, the natural gas flow that just will contain pollutant is fed to temperature swing adsorption system to remove moisture, and then it is fed to many beds, multi-layer vacuum pressure swing adsorption system, wherein removes nitrogen and oxygen from natural gas flow.
In this embodiment, can in Temp .-changing adsorption step and Vacuum Pressure Swing Adsorption step, use similar material described in three process.
In another embodiment of the present invention, a kind of deaerating type of cycles is disclosed.The natural gas flow that at first will comprise pollutant is fed to membrane module, removes carbon dioxide at this; Then this natural gas flow is fed to many beds, multi-layer vacuum pressure swing adsorption system, removes carbon dioxide and nitrogen at this.Then this natural gas flow is guided to liquefier, and then arrive oxygen disconnector tower, remove the remainder oxygen that natural gas flow, exists at this from natural gas, this remainder oxygen can be delivered to the oxygen storage system, be used for using later on.
In the present embodiment, before being fed to membrane module, at first trace contaminant is processed natural gas flow.Membrane module may be two or more films of single film or series connection.Membrane module can be removed carbon dioxide from natural gas flow, and the membrane material type that also can be depending on use is removed oxygen from natural gas flow.Natural gas flow is guided to many beds VSA system, and wherein each bed is multilayer laminated.These many beds, multilayer VSA system will generally include four adsorption bed.Yet, depend on that amount of pollutant and the power cost in the natural gas flow considered, can utilize more or less adsorption bed.Carry out stackedly for each bed, be used for to remove carbon dioxide, nitrogen or oxygen.In order to remove carbon dioxide, use the 13X molecular screen material.In order to remove nitrogen, use the titan silicate molecular screen material.Use has high carbon molecular sieve to oxygen affinity or other materials as the 3rd layer, and can determine this material by remove how much oxygen by membrane module.
Then, be fed to can be as filled type or disc type oxygen disconnector tower before, first natural gas flow is guided to liquefier.The remainder oxygen that in this removes natural gas, exists, and gather and remove natural gas, thereby storage.
Description of drawings
Fig. 1 illustrates the schematic diagram of the natural gas purification system that uses the monofilm assembly.
Fig. 2 illustrates the schematic diagram of the natural gas purification system that uses two membrane modules.
Fig. 3 illustrates the schematic diagram of the natural gas purification system that does not wherein have membrane module.
Fig. 4 illustrates the schematic diagram for the deaerating type of cycles of liquefied natural gas (LNG) production system.
The specific embodiment
With reference to figure 1, natural gas is fed to PSA drier bed A by pipeline 1, the water in this removing natural gas.Dry natural gas is fed to membrane type carbon dioxide removal unit C by pipeline 2, removes the most of carbon dioxide that exists in the natural gas flow at this.The infiltration natural gas is fed to other PSA drier beds B by pipeline 3, permeates natural gas with regenerator bed B at this.Adsorption bed A in the PSA system and the operation of B are such, and when adsorption bed A adsorbed water, adsorption bed B is by the infiltration natural gas regeneration from film unit C.When their role exchange, adsorption bed B will adsorb the water from natural gas flow, and adsorption bed A will be by the regeneration of infiltration natural gas.The natural gas flow of regeneration will leave adsorption bed B by pipeline 4, and can be used in generating.
Natural gas flow will leave membrane type carbon dioxide removal unit C by pipeline 5, and be fed to the D of VSA system.Each adsorption bed in four adsorption bed that exist in the VSA system has three layers---D1, D2 and D3.Four bed VSA systems are to have the typical recycling operation of one or two homogenizing.
Hereinafter express four circulation VSA techniques with a homogenization step.
ADS-absorption PP-cleans the R-repressurize temporarily
E-homogenizing P-cleans D-and empties
Hereinafter express four circulation VSA techniques with two homogenization step.
Bottom D1 is used for the carbon dioxide removal and can comprises sorbing material, such as the 13X zeolite.Second layer D2 is used for removing a large amount of nitrogen, and can comprise titan silicate/molecule grizzly, such as ETS-4.Top layer D3 is used for removing oxygen, and uses molecular screen material, such as carbon molecular sieve.The natural gas that does not now have carbon dioxide, nitrogen and oxygen leaves a VSA bed by pipeline 9.
In Fig. 2, except increasing by the second film unit, use identical Digital ID.Pipeline 31 is connected to the second film unit C1 with the first film unit C, and pipeline 51 will permeate Exhaust Gas and be transported to for discharging and/or the combined exhaust gas pipeline 8 of generating purpose.When using two groups of film units, second unit will help further to reduce the amount of carbon dioxide in the natural gas flow, and thereby may need less carbon dioxide removal material in the VSA system.
In Fig. 3, the carbon dioxide film unit that does not occur discussing among Fig. 1 and 2.Natural gas is fed to the adsorption bed G of TSA system by pipeline 10, at this from Adsorption Natural Gas water.Dry natural gas is fed to the I of VSA system from adsorption bed by pipeline 11.In the first adsorption bed in four adsorption bed indicating, I1 comprises for the material of removing nitrogen and can comprise titan silicate/molecule grizzly, such as ETS-4.Then, natural gas enters the top layer of adsorption bed I2, has the material that is used for removing oxygen at this, such as carbon molecular sieve.The natural gas that does not have oxygen and nitrogen will leave adsorption bed by pipeline 13.
The deoxygenation schematic diagram of producing liquified natural gas from natural gas feeding air-flow shown in Figure 4.Natural gas flow enters the first film L of film system by pipeline 20.Natural gas will pass pipeline 22 to second film unit M, and simultaneously, permeable for carbon dioxide will be left by pipeline 21, and it is guided for using subsequently, such as regeneration gas.The natural gas that will have great amount of carbon dioxide guides to many beds VSA N of system from film unit M by pipeline 24.Permeable for carbon dioxide and oxygen will leave the second film unit M by pipeline 23, and will be combined from the tail gas of the N of VSA system pipeline 25 and be combined as waste gas, and leave system by pipeline 26.Can be similar to four beds, the multilayer system of Fig. 1 and 2 in many beds VSA operation, but in this embodiment, adsorption bed comprises materials at two layers.Ground floor is used for removing carbon dioxide from natural gas flow, and the second layer is used for removing nitrogen from natural gas flow.
Natural gas flow will leave the VSA system by pipeline 27, and enter liquefier, make natural gas liquefaction at this.Mainly be that this liquefied natural gas stream with natural gas of some oxygen leaves liquefier by pipeline 20, and enter oxygen disconnector tower P.Disconnector tower P may be filled type or disc type destilling tower.Pipeline 20 passes heat exchanger Q and valve 20A.The oxygen of discharging leaves disconnector tower P by pipeline 32, and in one case, natural gas will leave by pipeline 31 with by heat exchanger Q, in heat exchanger Q, and will be with its further cooling before natural gas enters disconnector tower P again by pipeline 29.Reclaim liquefied natural gas by pipeline 30 and valve 30A.
Although described the present invention about specific embodiments of the invention, those skilled in the art should understand numerous other forms of the present invention and modification.Should the claim that the present invention is appended be interpreted as containing the obvious form of all these classes and modification in practicalness of the present invention and the scope.
Claims (27)
1. method that clears the pollution off from natural gas flow said method comprising the steps of:
The natural gas flow that a) will comprise pollutant is fed to drier;
B) described dry natural gas is flow to be given to membrane module, wherein remove carbon dioxide and oxygen from described natural gas flow; And
C) described natural gas flow is fed to many beds, multi-layer vacuum pressure swing adsorption system, wherein removes carbon dioxide, nitrogen and oxygen from described natural gas flow.
2. method according to claim 1 is characterized in that, selects described drier from the group of pressure-variable adsorption and Temp .-changing adsorption unit composition.
3. method according to claim 1 is characterized in that, the amount that described oxygen, nitrogen and carbon dioxide exist in described natural gas is respectively 0-5 molar percentage, 5-15 molar percentage and 30-45 molar percentage.
4. method according to claim 2 is characterized in that, described pressure-variable adsorption and described Temp .-changing adsorption unit comprise the activated alumina bed.
5. method according to claim 1 is characterized in that, described membrane module comprises above a membrane module.
6. method according to claim 1 is characterized in that, described film is modification doughnut polyamide nitrogen film.
7. method according to claim 1 is characterized in that, also comprises utilizing described membrane module to remove oxygen from described natural gas flow.
8. method according to claim 1 is characterized in that, described many beds, multi-layer vacuum pressure swing adsorption system comprise four adsorption bed.
9. method according to claim 8 is characterized in that, each adsorption bed in four adsorption bed comprises three layers.
10. method according to claim 9 is characterized in that, described three layers comprise respectively 13X molecular sieve, titan silicate sieve and carbon molecular sieve.
11. a method that clears the pollution off from natural gas flow said method comprising the steps of:
The described natural gas flow that a) will comprise pollutant is fed to drier; And
B) described dry natural gas is fed to many beds, multi-layer vacuum pressure swing adsorption system.
12. method according to claim 11 is characterized in that, described drier is temperature swing adsorption system.
13. method according to claim 12 is characterized in that, described temperature swing adsorption system comprises the activated alumina bed.
14. method according to claim 11 is characterized in that, described many beds, multi-layer vacuum pressure swing adsorption system comprise four adsorption bed.
15. method according to claim 14 is characterized in that, each adsorption bed in described four adsorption bed comprises three layers.
16. method according to claim 15 is characterized in that, described three layers comprise respectively 13X molecular sieve, titan silicate sieve and carbon molecular sieve.
17. the method from the natural gas flow deoxygenation said method comprising the steps of:
A) described natural gas flow is fed to membrane module;
B) described natural gas flow is fed to many beds, multi-layer vacuum pressure swing adsorption system;
C) described natural gas flow is fed to liquefier; And
D) described natural gas flow is fed to oxygen disconnector tower.
18. method according to claim 17 is characterized in that, described membrane module is removed carbon dioxide from described natural gas flow.
19. method according to claim 17 is characterized in that, described many beds, multi-layer vacuum pressure swing adsorption system are removed carbon dioxide and nitrogen from described natural gas flow.
20. method according to claim 17 is characterized in that, from the described oxygen disconnector tower natural gas of gathering.
21. method according to claim 17 is characterized in that, described membrane module comprises above a membrane module.
22. method according to claim 17 is characterized in that, described film is modification doughnut polyamide nitrogen film.
23. method according to claim 17, it also comprises and utilizes described membrane module to remove oxygen from described natural gas flow.
24. method according to claim 1 is characterized in that, described many beds, multi-layer vacuum pressure swing adsorption system comprise four adsorption bed.
25. method according to claim 24 is characterized in that, each adsorption bed in described four adsorption bed comprises two-layer.
26. method according to claim 25 is characterized in that, described two-layer 13X molecular sieve and the titan silicate sieve of comprising respectively.
27. method according to claim 17 is characterized in that, selects described oxygen disconnector tower from the group of filled type or disc type disconnector tower composition.
Applications Claiming Priority (5)
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US33197010P | 2010-05-06 | 2010-05-06 | |
US61/331,970 | 2010-05-06 | ||
US13/084,891 US20120085232A1 (en) | 2010-05-06 | 2011-04-12 | Methods for removing contaminants from natural gas |
US13/084,891 | 2011-04-12 | ||
PCT/US2011/032273 WO2011139500A1 (en) | 2010-05-06 | 2011-04-13 | Methods for removing contaminants from natural gas |
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CN102883791A true CN102883791A (en) | 2013-01-16 |
CN102883791B CN102883791B (en) | 2016-02-24 |
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EP (1) | EP2569077A4 (en) |
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US20170157555A1 (en) * | 2015-12-03 | 2017-06-08 | Air Liquide Advanced Technologies U.S. Llc | Method and system for purification of natural gas using membranes |
US10143970B2 (en) | 2016-08-09 | 2018-12-04 | Nrgtek, Inc. | Power generation from low-temperature heat by hydro-osmotic processes |
US9956522B2 (en) | 2016-08-09 | 2018-05-01 | Nrgtek, Inc. | Moisture removal from wet gases |
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FR3075658B1 (en) * | 2017-12-21 | 2022-01-28 | Air Liquide | METHOD FOR LIMITING THE CONCENTRATION OF OXYGEN CONTAINED IN A BIOMETHANE STREAM |
IT201900022983A1 (en) | 2019-12-04 | 2021-06-04 | Ab Impianti Srl | Plant and method for separating a gas mixture containing a plurality of components, in particular for obtaining biomethane |
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WO2011139500A1 (en) | 2011-11-10 |
CN102883791B (en) | 2016-02-24 |
US20120085232A1 (en) | 2012-04-12 |
EP2569077A1 (en) | 2013-03-20 |
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